CN113968986B - Preparation method of purple cabbage anthocyanin-collagen chitosan composite intelligent membrane - Google Patents
Preparation method of purple cabbage anthocyanin-collagen chitosan composite intelligent membrane Download PDFInfo
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- CN113968986B CN113968986B CN202111317094.1A CN202111317094A CN113968986B CN 113968986 B CN113968986 B CN 113968986B CN 202111317094 A CN202111317094 A CN 202111317094A CN 113968986 B CN113968986 B CN 113968986B
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- CIJQGPVMMRXSQW-UHFFFAOYSA-M sodium;2-aminoacetic acid;hydroxide Chemical compound O.[Na+].NCC([O-])=O CIJQGPVMMRXSQW-UHFFFAOYSA-M 0.000 description 1
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- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Storage Of Fruits Or Vegetables (AREA)
Abstract
The invention discloses a preparation method of a purple cabbage anthocyanin-collagen chitosan composite intelligent membrane, which comprises the following steps: preparing purple cabbage anthocyanin powder by utilizing purple cabbage; adding chitosan into acetic acid aqueous solution, adding collagen aqueous solution, then continuously adding glycerol and sodium citrate, heating in water bath, stirring, and cooling to obtain collagen chitosan solution; adding the purple cabbage anthocyanin powder into the collagen chitosan solution, uniformly stirring, standing for defoaming, injecting the obtained mixed solution into a mold, and drying to obtain the purple cabbage anthocyanin-collagen chitosan composite film. The purple cabbage anthocyanin-collagen chitosan composite intelligent film can be applied to fresh product freshness indication and fresh-keeping storage.
Description
Technical Field
The invention relates to the field of foods, in particular to preparation of a composite film.
Background
The fresh product is rich in unsaturated fatty acid and protein, and is easy to be affected by enzyme, oxygen and microorganism during processing and transportationProteolytic and lipoxidation occur with the release of volatile spoilage gases (which can lead to an increase in pH) which can lead not only to spoilage of the seafood but also to the production of harmful substances which affect the health of the consumer [1] Therefore, the development of the freshness indicating intelligent packaging material capable of intuitively feeding back the quality change information of the fresh product has important significance.
The freshness-indicating intelligent package is mainly used for monitoring the quality of food by adding a specific indicator which can react with volatile gas generated by food deterioration to generate color change, and the common chemical indicator materials on the market at present are methyl red, methyl orange, olfactory cresol blue and the like [2] . pH dyes, although stable in nature, present a safety hazard. In recent years, the development of active smart packages based on natural biopolymers has therefore become more and more important. Anthocyanin is a large class of plant-derived, natural, well-water-soluble polyphenols. Which is typically distributed among a variety of darker fruit, vegetable cell tissues. Anthocyanin has a variety of health benefits such as antioxidant, antibacterial, antidiabetic, antiobesity, anti-inflammatory, antiproliferative and anticancer activity. Among various biological properties of anthocyanin, its antioxidant and antibacterial activities are especially important for development of active package, and the use of film rich in anthocyanin can maintain food quality and prolong shelf life [3-4] . On the other hand, anthocyanin is very sensitive to changes in pH and presents different colors as pH changes, which enables anthocyanin-rich films to monitor the quality of packaged foods [5-6] . In conclusion, anthocyanin is an ideal raw material for developing an active intelligent packaging film, and can be used for preparing a fresh product and detecting the freshness of the fresh product together with a biodegradable material.
Reference is made to:
[1] xue the anthocyanin-based salmon freshness indicator packaging materials research [ D ]. University of Jiangsu, 2019;
[2] B.Kuswandi, A.Nurfawaidi.On-package dual sensors label based on pH indicators for real-time monitoring of beef freshness [ J ]. Food Control,2017,82:91-100 (B.Kuswandi, A.Nurfawaidi. real-time monitoring of beef freshness based on dual sensor tags [ J ]. Food Control,2017, 82:91-100);
[3] preparation of and characterization of intelligent starch/polyvinyl alcohol films for food packaging & Li, y.preparation and characterization of intelligent starch/PVA films for simultaneous colorimetric indication and antimicrobial activity for food packaging applications & carbohydrate, 2017,157,842-849;
[4] preparation of visual pH sensing films of Ma, Q., & Wang, L.preparation of a visual pH-sensing film based on tara gum incorporating cellulose and extracts from grape skin, sensors and Actuators B: chemical,2016,235,401-407 (Ma, Q., & Wang, L. Preparation of visual pH sensing films of the grape skin extract tara gum: sensor and actuator B: chemical,2016,235,401-407);
[5] carboxymethyl cellulose/starch and purple sweet potato (sweet potato) anthocyanin indicator film preparation and characterization for monitoring fish freshness;
[6] use of active chitosan/polyvinyl alcohol films with Cabbage anthocyanin as time-temperature indicator in smart food packaging food colloids,2015,43,180-188.
The problems of the current active intelligent package are as follows: (1) The matrix materials used for intelligent packaging mainly comprise protein and polysaccharide biopolymers, however, compared with synthetic polymers, the single protein films or polysaccharide films have the problems of higher water solubility, poorer mechanical properties and the like, and the problems limit the application of the single protein films or polysaccharide films in packaging materials. (2) Anthocyanins often exhibit low chemical stability and short half-life as well as relatively low bioavailability, and external factors such as pH, temperature, VC concentration, metal ion, oxygen concentration in the processing or storage environment affect their stability.
CN105111474a provides a preparation method of chitosan and gelatin composite membrane based on anthocyanin, firstly, obtaining solution containing proper anthocyanin concentration, then preparing chitosan mixed solution and gelatin solution; mixing the prepared chitosan mixed solution with gelatin solution, and magnetically stirring to obtain chitosan/gelatin mixed solution; and fully mixing the obtained solution containing the anthocyanin concentration with the chitosan/gelatin mixed solution, casting the obtained solution into a glass plate, naturally airing or drying, drying to prepare a film, and removing the film to obtain the composite film to be prepared. The method combines natural pigment with natural polymer materials such as chitosan gelatin and the like, has the excellent characteristics of the natural pigment and the chitosan gelatin, is a green packaging material, realizes the combination of freshness indication and the packaging material, is safer than a single indicator card made of toxic biological dye, and is a packaging material which can be used for preserving freshness. However, the invention has certain problems that firstly, the anthocyanin stability in the prepared composite material is not high, and a good indication effect is obtained only in a very short time; secondly, sodium tripolyphosphate is used as a cross-linking agent, and is commonly used in industrial products, and has great harm to health after long-term contact, so that the sodium tripolyphosphate is applied to an indication film, particularly to the food industry, and the safety is required to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a purple cabbage anthocyanin-collagen chitosan intelligent packaging film.
In order to solve the technical problems, the invention provides a preparation method of a purple cabbage anthocyanin-collagen chitosan intelligent packaging film, which comprises the following steps:
1) Preparation of purple cabbage anthocyanin powder:
preparing purple cabbage anthocyanin powder by utilizing purple cabbage;
2) Preparation of collagen chitosan solution:
adding 1-5 g of chitosan into 100-500 mL of acetic acid aqueous solution, stirring and dissolving, standing for 10-14 hours (standing overnight), adding 20-500 mL of collagen aqueous solution, then continuously adding glycerol and sodium citrate, heating and stirring in a water bath, and cooling (cooling to room temperature) to obtain collagen chitosan solution;
the volume concentration of acetic acid in the acetic acid aqueous solution is 0.8-1.2%, and the concentration of collagen in the collagen aqueous solution is 2-6 g/100mL;
the addition amount of the glycerol is 15-45% of the total mass of the collagen and the chitosan (total dry mass), and the sodium citrate is as follows: (sum of acetic acid aqueous solution and collagen aqueous solution volume) =feed liquid ratio of 0.1-1 mg/mL;
3) Preparation of purple cabbage anthocyanin-collagen chitosan composite film:
adding purple cabbage anthocyanin powder into the collagen chitosan solution obtained in the step 2), uniformly stirring, standing for defoaming, injecting the obtained mixed solution into a mold, and drying to obtain a purple cabbage anthocyanin-collagen chitosan composite film (CA-CS-RCE);
the dosage of the purple cabbage anthocyanin powder is 1-5% of the total mass of the collagen and the chitosan (total dry mass) in the step 2).
As an improvement of the preparation method of the purple cabbage anthocyanin-collagen chitosan composite intelligent membrane, the step 1) is as follows:
firstly, carrying out enzyme deactivation treatment on fresh purple cabbage, then, carrying out juice extraction, leaching the juice obtained by juice extraction by using an ethanol water solution, filtering, centrifuging at a low temperature, taking supernatant, carrying out rotary evaporation, standing at a low temperature, and carrying out vacuum freeze drying to obtain purple cabbage anthocyanin powder;
the method comprises the following steps:
the enzyme deactivation treatment is to deactivate enzyme at 100+ -5deg.C for 5+ -0.5 min;
the volume concentration of ethanol in the ethanol water solution is (65+/-5)%; when leaching, the volume ratio of the slurry to the ethanol water solution is 1 (5+/-1), the extraction temperature is 50+/-5 ℃ and the extraction time is 2+/-0.2 h;
the low-temperature centrifugation is as follows: centrifuging at the centrifugal speed of 6000-10000 rpm for 10-20 minutes at the temperature of 4-25 ℃;
the rotary evaporation temperature is 30-50 ℃ and the rotating speed is 10-40 rpm;
placing at a low temperature of-18+/-5 ℃ for 24-48 hours;
vacuum freeze drying is as follows: drying at-20 to-50 deg.c and air pressure of 20-200 Pa for 24-48 hr.
As a further improvement of the preparation method of the purple cabbage anthocyanin-collagen chitosan composite intelligent membrane, in the step 2), the following steps are adopted:
adding chitosan into acetic acid water solution, and stirring for 1-2 hours at a stirring speed of 100-800 rpm;
the water bath heating and stirring steps are as follows: stirring at 25-75 deg.c and 100-800 rpm for 0.5-2 hr.
As a further improvement of the preparation method of the purple cabbage anthocyanin-collagen chitosan composite intelligent membrane, the step 3) is as follows:
stirring for 1-4 hours at a stirring speed of 100-800 rpm;
standing for defoaming for 2-4 hours;
drying is carried out for 24-48 hours at 20-50 ℃.
According to the invention, collagen and chitosan are compounded to prepare the protein-polysaccharide binary composite membrane, and an ionic crosslinking method is adopted to further reduce the water solubility of the collagen-chitosan composite membrane, and simultaneously improve the mechanical properties of the composite membrane. In addition, collagen and chitosan are combined for encapsulating anthocyanin, so that stability and accuracy of anthocyanin serving as a pH indicator in an intelligent packaging film system are improved (figures 5 and 6). The thickness of the composite film can be set according to practical needs, and is generally about 0.08 + -0.02 mm.
Compared with the prior art, the invention has the following advantages:
(1) Purple cabbage is an anthocyanin-rich plant. From the molecular structure, the stability of anthocyanin extracted from the purple cabbage is higher than that of other varieties. Because the purple cabbage anthocyanin has the characteristic of high acylation, the acylated anthocyanin has stronger stability to heat and light, higher antioxidation capability and wider pH dependent chromatography, and therefore, compared with the anthocyanin from purple sweet potatoes, black rice, eggplants and the like, the anthocyanin from the purple cabbage shows better performance in terms of pH sensitivity.
(2) The chitosan molecule has reactive functional groups, so that the chitosan has excellent gel property, high adsorptivity and biodegradability, and can effectively inhibit bacteria and fungi. In addition, chitosan has good film forming property, so that the chitosan is an important raw material in preparing food-grade packaging materials. The collagen has the characteristics of good biocompatibility, water retention, stability, edibility and the like, and is considered to be the polymer with the most research significance and the most research value in organisms. The collagen chitosan matrix membrane prepared by the invention not only has the advantages of a chitosan membrane, but also has excellent water holding capacity, biocompatibility and safety of the collagen membrane, so that the collagen chitosan composite membrane has natural advantages when being used as a packaging material of fresh products.
(3) The sodium citrate is safe and nontoxic, biodegradable, and the usage amount of the sodium citrate in food can be determined according to the normal production requirement in China's food additive use sanitary Standard. The sodium citrate is added into the purple cabbage anthocyanin-collagen chitosan composite film as an ion crosslinking agent, so that the mechanical property of the composite film can be improved, the water solubility of the composite film can be obviously reduced, the sodium citrate promotes the crosslinking between chitosan molecules and collagen molecules and between chitosan molecules, and the mobility between molecules is reduced, and therefore, the tensile strength of the composite material is improved, and the mechanical property of the composite film is effectively improved. In addition, the addition of sodium citrate also obviously reduces the water solubility of the composite membrane, because the citrate and chitosan protonated amino groups have electrostatic interaction, free amino groups are fixed, the structure of the membrane is more stable, and the water solubility is greatly reduced.
(4) On one hand, the addition of the purple cabbage anthocyanin not only improves the oxidation resistance and bacteriostasis of the composite membrane, but also plays a role of a cross-linking agent as natural polyphenol, so that the water solubility of the collagen chitosan composite membrane is further reduced, and the hydrophilic groups in the collagen chitosan binary composite membrane are more, so that the collagen chitosan composite membrane is better in hydrophilicity, and poor in water resistance, after the anthocyanin is added, the hydrogen bond acting force between collagen and chitosan molecules is enhanced, and the ratio of the hydrophilic groups in the composite membrane is relatively reduced, so that the water resistance of the composite membrane is improved. On the other hand, collagen contains a large amount of proline, so that the collagen has strong affinity with polyphenols, can self-assemble with anthocyanin to form nano particles, and has certain stabilizing and controlled release effects on the anthocyanin. After the collagen and the chitosan are combined, the chitosan not only can form self-aggregation micelle to encapsulate the anthocyanin through hydrophobic interaction, but also can weaken strong interaction between the collagen and the anthocyanin through an electrostatic assembly method with the collagen, so that the nanoparticle is prevented from flocculating, the stability of the nanoparticle is improved, the long-acting slow-release effect on the anthocyanin is achieved, and the stability of the anthocyanin is further improved.
In summary, the visual intelligent packaging film is prepared by taking collagen and chitosan as matrix films and taking the natural polyphenol substance-purple cabbage anthocyanin as a pH indicator, so that the food packaging film has good mechanical property, biocompatibility, thermal stability and pH sensitivity, can be applied to fresh product freshness indication and fresh-keeping storage, provides important technical parameters and reference materials for development of novel visual intelligent fresh-keeping technology, and further expands the application of the natural polyphenol substance in the field of food packaging.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a Fourier infrared plot of purple cabbage anthocyanin-collagen chitosan composite film, collagen chitosan film, purple cabbage anthocyanin, collagen and chitosan;
FIG. 2 is an SEM image of collagen chitosan composite membrane and collagen chitosan (CA-CS) membrane with different amounts of purple cabbage anthocyanin (RCE) addition;
FIG. 3 is an X-ray diffraction pattern of purple cabbage anthocyanin-collagen chitosan composite film, collagen chitosan film, and purple cabbage anthocyanin;
FIG. 4 is a graph of thermal stability (DSC) analysis of purple cabbage anthocyanin-collagen chitosan composite membranes and collagen chitosan membranes;
FIG. 5 is a graph showing the sensitivity of color change of the purple cabbage anthocyanin-collagen chitosan composite film under different pH buffer conditions;
FIG. 6 is a color difference plot of the purple cabbage anthocyanin-collagen chitosan composite film (4 ℃) within 14 days;
FIG. 7 is a graph showing the color index change of the collagen chitosan composite film during the shrimp freshness monitoring process (0-6 days);
FIG. 8 is a graph showing the total color difference change of the collagen chitosan composite film in the shrimp freshness monitoring process (0-6 days);
FIG. 9 is a graph showing the effect of different amounts of ionic crosslinking agent on the water solubility of the purple cabbage anthocyanin-collagen chitosan composite film.
FIG. 10 is a graph showing the comparison of the surfaces (a, b) and the cross sections (c, d) of the anthocyanin-gelatin chitosan composite membrane (GEL-CA-RCE 3%) and the anthocyanin-collagen chitosan composite membrane (CA-CS-RCE 3%).
Detailed Description
Example 1, a preparation method of a purple cabbage anthocyanin-collagen chitosan composite intelligent membrane sequentially comprises the following steps:
1) Preparation of purple cabbage anthocyanin (RCE) powder:
the preparation method comprises the steps of carrying out enzyme deactivation treatment on 500g of fresh purple cabbage, then carrying out juice extraction, leaching the juice obtained by juice extraction by using an ethanol water solution, filtering, centrifuging at a low temperature, taking supernatant, carrying out rotary evaporation, standing at a low temperature for 24-48 hours, and then carrying out vacuum freeze-drying to obtain purple cabbage anthocyanin powder (about 10 g).
Wherein:
the enzyme deactivation temperature is 100 ℃ and the duration is 5 minutes;
the volume ratio of absolute ethyl alcohol and deionized water in the ethyl alcohol aqueous solution is 65:35, the extraction feed liquid ratio is 1:5, namely, the slurry obtained by juice extraction: ethanol aqueous solution=1:5 volume ratio, extraction temperature is 50 ℃, time is 2h;
low temperature centrifugation: the speed is 8000 rpm, the centrifugation time is 15 minutes, and the centrifugation temperature is 4 ℃; the purpose of low-temperature centrifugation is to prevent anthocyanin from being decomposed by heat;
the rotary evaporation temperature is 35 ℃, and the rotating speed is 20 revolutions per minute;
the temperature for low-temperature placement is-18 ℃;
the vacuum freeze drying temperature is-50 ℃, the air pressure is 20 Pa, and the time is 24-48 hours.
The process temperatures, which are not explicitly stated above, such as juice extraction, leaching, filtration, etc., are carried out at room temperature (20-25 ℃).
2) Preparation of collagen chitosan (CA-CS) solution:
2g of Chitosan (CS) was dissolved in 100mL of an aqueous acetic acid solution and stirred at 300 rpm for 1 hour to allow CS to be sufficiently dissolved, then allowed to stand overnight (i.e., allowed to stand for 10 to 14 hours), followed by the addition of 25mL of a Collagen (CA) solution having a solids content of 4% (i.e., 4g/100 mL), then continued to add 0.9g of glycerol, 0.075g of sodium citrate anhydrous, heated in a water bath and stirred (300 rpm, 55 ℃ C., 1 hour), and cooled to room temperature to give a collagen chitosan (CA-CS) solution, about 125mL, ready for use.
The acetic acid solution is 1% acetic acid aqueous solution by volume, namely, acetic acid: deionized water = 1:99 volume ratio of the mixed solution;
in this step, sodium citrate: (sum of acetic acid aqueous solution and collagen aqueous solution volume) =0.6 mg/mL of feed liquid ratio;
glycerol: (collagen+chitosan) =30%; that is, the amount of glycerol added was 30% of the total mass of collagen and chitosan (total dry matter);
3) Preparation of purple cabbage anthocyanin-collagen chitosan composite film (CA-CS-RCE):
adding 30mg of purple cabbage anthocyanin powder into the collagen chitosan (CA-CS) solution (about 125 mL) obtained in the step 2), uniformly stirring (300 rpm, 4 hours), standing for 2-4 hours to remove foam, pouring 20mL of mixed solution into a plastic culture dish with the diameter of 90mm, and drying at 30 ℃ for 24 hours to obtain the purple cabbage anthocyanin-collagen chitosan composite film (hereinafter referred to as composite film), wherein the thickness of the composite film is about 0.08mm.
In this example 1, the purple cabbage anthocyanin powder was 1% of the sum of the masses of collagen and chitosan, and thus the resulting composite film was named CA-CS-RCE 1%.
Preparation of control, collagen chitosan Complex Membrane (CA-CS)
The use of 30mg of purple cabbage anthocyanin powder in the step 3) is eliminated, namely, the collagen chitosan (CA-CS) solution obtained in the step 2) in the example 1 is directly stirred uniformly and then is placed still, and the rest is the same as the step 3) in the example 1, so that the collagen chitosan (CA-CS) film is obtained.
Example 2, a method for preparing a purple cabbage anthocyanin-collagen chitosan composite intelligent film:
the amount of purple cabbage anthocyanin powder in example 1, step 3) was changed from 30mg to 60mg, the remainder being identical to example 1.
In this example 2, the purple cabbage anthocyanin powder was 2% of the sum of the masses of collagen and chitosan, and thus the resulting composite film was named CA-CS-RCE 2%.
Example 3, a method for preparing a purple cabbage anthocyanin-collagen chitosan composite intelligent film:
the amount of purple cabbage anthocyanin powder in example 1, step 3) was changed from 30mg to 90mg, the remainder being identical to example 1.
In this example 3, the purple cabbage anthocyanin powder was 3% of the sum of the masses of collagen and chitosan, and thus the resulting composite film was named CA-CS-RCE 3%.
Experiment 1 the composite films (CA-CS-RCE 1%, CA-CS-RCE 2%, CA-CS-RCE 3%) obtained in examples 1 to 3, and collagen chitosan (CA-CS) film, purple cabbage anthocyanin (RCE) powder, chitosan (CS) and Collagen (CA) were examined by a Fourier transform infrared spectrometer (FTIR) to obtain Fourier infrared images, as shown in FIG. 1.
From fig. 1, it can be known that: anthocyanin can be bound to collagen chitosan through hydrogen bonding, hydrophobic interactions or electrostatic interactions.
Experiment 2 the composite films (CA-CS-RCE 1%, CA-CS-RCE 2%, CA-CS-RCE 3%) and collagen chitosan (CA-CS) films obtained in examples 1 to 3 were examined by a Scanning Electron Microscope (SEM), and the SEM images obtained are shown in FIG. 2.
From fig. 2, it can be known that: when a small amount of purple cabbage anthocyanin extract is added into the collagen chitosan film, the composite film does not have obvious granular feel, which indicates that anthocyanin can be well fused into the collagen chitosan film.
Experiment 3 the composite films (CA-CS-RCE 1%, CA-CS-RCE 2%, CA-CS-RCE 3%) and collagen chitosan (CA-CS) films, and purple cabbage anthocyanin (RCE) powders obtained in examples 1 to 3 were examined by an X-ray diffractometer, and the X-ray diffraction patterns obtained were shown in FIG. 3.
According to an X-ray diffraction pattern, the anthocyanin changes the crystal structure of the collagen chitosan binary composite film, the anthocyanin-collagen chitosan composite film is not simply overlapped by three substances of anthocyanin, collagen and chitosan, certain interactions such as hydrogen bonds, electrostatic interactions and the like occur, and the diffraction peak intensity is obviously weakened along with the increase of the addition amount of the anthocyanin, so that the interaction between the anthocyanin and the collagen chitosan is stronger, and the three substances are combined more tightly.
In conclusion, through infrared spectrum, a scanning electron microscope and X-ray diffraction identification, the purple cabbage anthocyanin can be effectively combined with collagen chitosan.
Experiment 4, thermal stability:
the composite films (CA-CS-RCE 1%, CA-CS-RCE 2%, CA-CS-RCE 3%) and collagen chitosan (CA-CS) films obtained in examples 1 to 3 were subjected to thermal stability test, and the thermal stability test was carried out according to GB/T19466.1-2004, and the resulting thermal stability (DSC) analysis chart was shown in FIG. 4.
From fig. 4, it can be known that:
the composite films obtained in examples 1 to 3 were enhanced in thermal stability,
relative to the melting temperature of CA-CS (121.5 ℃):
the melting temperature of CA-CS-RCE was increased by 9.1℃at 1%.
The melting temperature of CA-CS-RCE was increased by 2% by 6 ℃.
The melting temperature of CA-CS-RCE was increased by 2.2℃at 3%.
Experiment 5 the purple cabbage anthocyanin-collagen chitosan composite films obtained in examples 1 to 3 and the collagen chitosan films obtained in examples 3 were examined by a texture analyzer according to ASTM standard method D882-91 (astm.2003), respectively, and the results were shown in table 1 below:
TABLE 1 mechanical Properties (tensile Strength and elongation at break) of purple cabbage anthocyanin-collagen Chitosan composite film and collagen Chitosan film
CA-CS-RCE 1% of example 1 (purple cabbage anthocyanin addition 0.24 g/L) versus collagen chitosan film alone: the maximum tensile strength is improved by 5.4 percent, and the elongation at break is improved by 8.4 percent;
CA-CS-RCE 2% of example 2 (purple cabbage anthocyanin addition 0.48 g/L) versus collagen chitosan film alone: the maximum tensile strength is reduced by 3.6 percent, and the elongation at break is improved by 2.9 percent;
CA-CS-RCE3% of example 3 (purple cabbage anthocyanin addition 0.72 g/L) versus collagen chitosan film alone: the maximum tensile strength is reduced by 7.2%, and the elongation at break is reduced by 9.9%.
Experiment 6, reference (casarigo a., souza)W.S., cerqueira M.A., et al, chitosan/clay films 'properties as affected by biopolymer and clay micro/nanoparticles' concentrations.food hydrosol ids,2009.23 (7), 1895-1902), the purple cabbage anthocyanin-collagen chitosan composite films obtained in examples 1-3 were tested for solubility in water; solubility (%) = [ (m) 2 -m 1 )/m 1 ]×100;
m 1 : drying the film in a dryer to a constant weight mass (g);
m 2 the film was dissolved in 100mL of distilled water at room temperature for 12h and dried in an oven at 60℃to a constant weight mass (g).
The results obtained were:
the CA-CS-RCE of example 1 had a solubility in water of 33.7%,
the CA-CS-RCE 2% of example 2, the solubility in water was 32.1%,
the CA-CS-RCE3% of example 3 had a solubility in water of 34.8%.
Experiment 7, detecting color change of the purple cabbage anthocyanin-collagen chitosan composite film under the conditions of different pH value buffers:
setting pH 3-pH 11 standard buffer solution (glycine-hydrochloric acid buffer solution with pH3-4, disodium hydrogen phosphate-citric acid buffer solution with pH5-8, glycine-sodium hydroxide buffer solution with pH9-10, sodium bicarbonate-sodium hydroxide buffer solution with pH 11), wherein the soaking time of the composite membrane in the buffer solution is 5min, and the temperature is room temperature; and taking out, observing the color change, collecting the color change picture by a camera, extracting R, G and B values of a control group (the composite film which is not treated by the buffer solution) and the composite film which is soaked by the buffer solutions with different pH values, and calculating the sensitivity (S) by the following formula.
Wherein R is a ,G a ,B a Characteristic values after treatment by different pH buffers; r is R b ,G b ,B b For the characteristic values of the control group, deltaR, deltaG and DeltaB correspond to characteristic difference values after treatment by different pH buffers before and after treatment.
When the pH of the buffer is between 3 and 5, the composite membrane appears to be purple-red, and as the pH decreases, the red color is more pronounced. When the pH of the buffer solution is between 6 and 7, the composite membrane is purple. When the pH of the buffer solution is between 8 and 9, the composite membrane has bluish violet color, and the blue color deepens as the pH increases. When the pH of the buffer solution is between 10 and 11, the composite membrane is blue-green.
Fig. 5 is a color change sensitivity chart; as can be seen from fig. 5: the sensitivity of the composite membrane in alkaline environment is higher than that in acid environment. When the addition amount of the anthocyanin is 2%, the sensitivity of the anthocyanin under alkaline environment is highest, namely about 63%, and the anthocyanin is suitable for freshness indication of fresh meat products.
Experiment 8, color stability (4 ℃ C.)
The experimental content is specifically as follows: the purple cabbage anthocyanin-collagen chitosan composite film was left at 4℃for 14 days, wherein the L, a, b values thereof were measured with a color difference meter every 2 days, and the total color difference was calculated. The calculation formula of the total color difference (Δe) is as follows;
△E=(△L 2 +△a 2 +△b 2 )^ 1/2
△L=L-L 0 ;△a=a-a 0 ;△b=b-b 0
l, a, b are characteristic values of the composite membrane after being placed for 2-14 days at 4 ℃, L 0 ,a 0 ,b 0 Is the initial characteristic value, namely, the characteristic value of the composite film on the 0 th day.
The color stability (4 ℃) comparison chart of the obtained purple cabbage anthocyanin-collagen chitosan composite film is shown in fig. 6.
As can be seen from fig. 6: the composite film has better color stability, and when the addition amount of anthocyanin is 2% or 3%, the color difference value shows a tendency to decrease after the 8 th day, so that the color of the composite film is in a more stable state after the 8 th day.
Experiment 9 food spoilage
Cutting composite membrane CA-CS-RCE3% after standing at 4deg.C for 14 days into square with side length of 1.5cm, attaching it on top of culture dish containing shrimp, standing at 4deg.C for 6 days, observing and recording change of composite membrane L, a, b, and delta E value with color difference meter, and performing control experiment, recording as L 0 、a 0 、b 0 、ΔE 0 The values are shown in FIGS. 7 to 8.
Volatile basic nitrogen values (TVB-N), pH values, total colony count (TMC) and thiobarbituric acid values (TBARS) of shrimp were determined according to GB/T35252-2017, GB 5009.228-2016, GB 4789.2-2016, GB 5009.237-2016, respectively. The results obtained are shown in Table 2.
TABLE 2 shrimp fresh index volatile basic Nitrogen, fat Oxidation value, colony count and pH Change during storage of shrimp at 4 ℃ (0-6 days)
In Table 2, the shrimp freshness index volatile basic nitrogen, TBARS value and TMC value change significantly over time, pH value change significantly over 0-2 days and not over 3-6 days.
As shown in figures 7-9, on day 0, the color difference index of the experimental group is close to that of the control group, the L value is reduced within 0-2 days, the values of a, b and delta E are increased, the film color of the experimental group is changed from purple red to dark purple, the L value is gradually increased within 2-6 days, the a is gradually reduced, the color becomes bright, the red is gradually faded, and the blue is more obvious. The color parameters of the control group film have no obvious change within 0-6 days, the total color difference is less than 4, and the control group film has obvious difference from the experimental group.
The putrefactive gas such as ammonia gas, trimethylamine and the like reacts with water in the environment to raise the pH of the environment and create an alkaline environment, and it is known from the above experiment 7 that the color change sensitivity of the composite film is high in the alkaline environment, so it can be concluded that: is sensitive to spoilage gases of fresh produce.
In conclusion, the purple cabbage anthocyanin-collagen chitosan composite films obtained in the examples 1-3 are sensitive to putrefactive gas of fresh products, have good color stability at 4 ℃, show obvious color reaction in 7 days under different pH values, and can be applied to freshness indication of fresh meat products. The color change of the composite film has good correlation with the shrimp freshness index, which indicates that the composite film has good freshness indication effect.
Comparative example 1:
sodium citrate as in step 2) of example 1: the ratio (mg/mL) of feed solution (sum of acetic acid aqueous solution and collagen aqueous solution volume) was changed from 0.6 to 0,0.2,0.4, 0.8,1, respectively, and the remainder was the same as in example 1.
The composite film was tested for water solubility according to experiment 6, and the results are shown in FIG. 9.
The composite film obtained without sodium citrate (i.e., with a feed-liquid ratio of 0) is named as composite film a, the solubility in water is 63.2%, and when the composite film is in a humid environment for a long time, the surface of the composite film is slightly wrinkled, because the composite film a absorbs water and swells, the mechanical strength of the film is weakened, the film is easy to break, the appearance is poor, and the application of the film serving as an indication film is affected.
When the addition amount of sodium citrate is 0.6mg/mL, the water solubility is greatly reduced compared with the composite film with the addition amount of 0.2 and 0.4mg/mL, the tensile strength is improved, and the ductility (elongation at break) is better than that of the composite film with the addition amount of 0.8 and 1.0mg/mL, so that the composite film is suitable for the requirement of the freshness indication of the water product in the practical application of the invention.
The composite film a was tested as described in experiment 5, with the following results: the tensile strength of the composite film A is 8.86+/-0.79 Mpa, and the elongation at break is 89.63%. Thus, the maximum tensile strength of composite film A was reduced by 34.1% and the elongation at break was increased by 57.2% relative to the CA-CS-RCE 1% obtained in example 1.
The composite film A is identified by an atomic force microscope through infrared spectrum and X-ray diffraction and a scanning electron microscope, and the purple cabbage anthocyanin can be effectively combined with the collagen chitosan; the product is sensitive to spoilage gases of fresh products, has good color stability at 4 ℃ and shows obvious color reaction under different pH values within 7 days.
It is therefore known that: sodium citrate only affects the water solubility and mechanical properties of the composite film, and hardly affects the color development effect.
Comparative example 2 the remainder was identical to example 1 except that "25mL of the Collagen (CA) solution having a solids content of 4% in example 3 was" changed to "25mL of the gelatin solution having a solids content of 4%.
The resulting product was designated GEL-CS-RCE 3%.
According to experiment 2, the microscopic morphology of the anthocyanin-gelatin chitosan composite film (GEL-CS-RCE 3%) was examined, and as shown in FIG. 10, the anthocyanin-gelatin chitosan composite film (GEL-CS-RCE 3%) exhibited a gully-like shape in the microscopic morphology, and the roughness of the cross section was higher than that of example 3.
According to experiment 3, the mechanical properties of the composite film are detected, the tensile strength is 20.3+/-1.3 Mpa, the elongation at break is 13.2+/-2.1%, and the ductility is reduced by 72.0% compared with that of the composite film in example 3.
According to experiment 7, the pH sensitivity of the anthocyanin-gelatin chitosan composite film is detected to obtain a result of 17.2% -22.5%, so that the sensitivity is lower than that of example 3.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (3)
1. The preparation method of the purple cabbage anthocyanin-collagen chitosan composite intelligent membrane is characterized by comprising the following steps of:
1) Preparation of purple cabbage anthocyanin powder:
preparing purple cabbage anthocyanin powder by utilizing purple cabbage;
2) Preparation of collagen chitosan solution:
adding 1-5 g of chitosan into 100-500 mL of acetic acid aqueous solution, stirring and dissolving, standing for 10-14 hours, adding 20-500 mL of collagen aqueous solution, continuously adding glycerol and sodium citrate, heating in a water bath, stirring, and cooling to obtain collagen chitosan solution;
the volume concentration of acetic acid in the acetic acid aqueous solution is 0.8-1.2%, and the concentration of collagen in the collagen aqueous solution is 2-6 g/100mL;
the addition amount of the glycerol is 15% -45% of the total mass of the collagen and the chitosan, and the sodium citrate is as follows: (sum of acetic acid aqueous solution and collagen aqueous solution volume) =feed-liquid ratio of 0.1-1 mg/mL;
adding chitosan into an acetic acid aqueous solution, and stirring for 1-2 hours at a stirring speed of 100-800 rpm;
the water bath heating and stirring steps are as follows: stirring at the temperature of 25-75 ℃ for 0.5-2 hours at the speed of 100-800 rpm;
3) Preparation of purple cabbage anthocyanin-collagen chitosan composite film:
adding purple cabbage anthocyanin powder into the collagen chitosan solution obtained in the step 2), uniformly stirring, standing for defoaming, injecting the obtained mixed solution into a mold, and drying to obtain the purple cabbage anthocyanin-collagen chitosan composite film;
the dosage of the purple cabbage anthocyanin powder is 2% of the sum of the masses of the collagen and the chitosan in the step 2);
stirring for 1-4 hours at a stirring speed of 100-800 rpm;
standing for defoaming for 2-4 hours;
drying is carried out for 24-48 hours at 20-50 ℃.
2. The method for preparing the purple cabbage anthocyanin-collagen chitosan composite intelligent membrane according to claim 1, wherein the step 1) is as follows:
and (3) performing enzyme deactivation treatment on fresh purple cabbage, then squeezing juice, leaching the juice with an ethanol water solution, filtering, centrifuging at a low temperature, taking supernatant, performing rotary evaporation, standing at a low temperature, and performing vacuum freeze drying to obtain purple cabbage anthocyanin powder.
3. The method for preparing the purple cabbage anthocyanin-collagen chitosan composite intelligent membrane according to claim 2, wherein in the step 1):
the enzyme deactivation treatment is to deactivate enzyme at 100+ -5deg.C for 5+ -0.5 min;
the volume concentration of ethanol in the ethanol water solution is (65+/-5)%; when leaching, the volume ratio of the slurry to the ethanol water solution is 1 (5+/-1), the extraction temperature is 50+/-5 ℃ and the extraction time is 2+/-0.2 h;
the low-temperature centrifugation is as follows: centrifuging for 10-20 minutes at the centrifugal speed of 6000-10000 revolutions per minute at the temperature of 4-25 ℃;
the rotary evaporation temperature is 30-50 ℃, and the rotating speed is 10-40 revolutions per minute;
placing at a low temperature of-18+/-5 ℃ for 24-48 hours;
vacuum freeze drying is as follows: and (3) drying for 24-48 hours at the temperature of minus 20-50 ℃ and the air pressure of 20-200 Pa.
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